Composition for dyeing keratin fibres with a cationic direct dye and a thickening polymer

ABSTRACT

The invention relates to a composition for dyeing fibers such as the hair, comprising at least one cationic direct dye of given formula, and which also contains at least one thickening polymer chosen from the group comprising:—nonionic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain,—anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain,—cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain. The invention also relates to the dyeing processes and dyeing kits therefor.

The invention relates to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising, in a medium which is suitable for dyeing, at least one cationic direct dye of given formula and at least one specific thickening polymer.

The invention also relates to the dyeing processes and dyeing devices using the said composition.

Two types of dyeing may be distinguished in the haircare sector.

The first is semi-permanent or temporary dyeing, or direct dyeing, which uses dyes capable of giving the hair a natural coloration, a more or less pronounced colour change which may withstand shampooing several times. These dyes are also known as direct dyes; they can be used with or without an oxidizing agent. In the presence of an oxidizing agent, the aim is to obtain lightening dyeing. Lightening dyeing is carried out by applying a mixture, prepared at the time of use, of a direct dye and an oxidizing agent to the hair, and makes it possible in particular to obtain, by lightening the melanin in the hair, an advantageous effect such as a unified colour in the case of grey hair, or to bring out the colour in the case of naturally pigmented hair.

The second is permanent dyeing or oxidation dyeing. This is carried out with so-called “oxidation” dyes comprising oxidation dye precursors and couplers. Oxidation dye precursors, commonly known as “oxidation bases”, are compounds which are initially colourless or weakly coloured which develop their dyeing power on the hair in the presence of oxidizing agents added at the time of use, leading to the formation of coloured compounds and dyes. The formation of these coloured compounds and dyes results either from an oxidative condensation of the “oxidation bases” with themselves or from an oxidative condensation of the oxidation bases with coloration-modifying compounds commonly known as “couplers”, which are generally present in the dye compositions used in oxidation dyeing.

It is known practice to add direct dyes to oxidation dyes in order to vary the shades obtained with the said oxidation dyes or to enrich the shades with glints.

Among the cationic direct dyes available in the sector of dyeing keratin fibres, in particular human keratin fibres, the compounds whose structure is developed in the text hereinbelow are already known; nevertheless, these dyes lead to colorations which have characteristics that are still unsatisfactory as regards the intensity, the homogeneity of the colour distributed along the fibre, in which case the coloration is said to be too selective, and as regards the staying power, in terms of the resistance to the various attacking factors to which the hair may be subjected (light, bad weather, shampooing).

After considerable research conducted in this matter, the Applicant has now discovered that it is possible to obtain novel compositions for dyeing keratin fibres which are capable of giving more intense and yet unselective colorations which show good resistance to the various attacking factors to which the hair may be subjected, by combining at least one specific thickening polymer with at least one known cationic direct dye of the prior art, which have the respective formulae defined below.

This discovery forms the basis of the present invention.

A first subject of the present invention is thus a composition for dyeing keratin fibres, and in particular human keratin fibres such as the hair, containing, in a medium which is suitable for dyeing, (i) at least one cationic direct dye whose structure corresponds to formulae (I) to (IV) defined below, characterized in that it also contains (ii) at least one specific thickening polymer.

(i) The cationic direct dye which can be used according to the present invention is a compound chosen from those of formulae (I), (II), (III), (III′) and (IV) below:

-   -   a) the compounds of formula (I) below:         in which:

-   D represents a nitrogen atom or a —CH group,

-   R₁, and R₂, which may be identical or different, represent a     hydrogen atom; a C₁-C₄ alkyl radical which can be substituted with a     —CN, —OH or —NH₂ radical or form, with a carbon atom of the benzene     ring, a heterocycle optionally containing oxygen or nitrogen, which     can be substituted with one or more C₁-C₄ alkyl radicals; a     4′-aminophenyl radical,

-   R₃ and R′₃, which may be identical or different, represent a     hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine     and fluorine, a cyano radical, or a C₁-C₄ alkyl, C₁-C₄ alkoxy or     acetyloxy radical,

-   X⁻ represents an anion preferably chosen from chloride, methyl     sulphate and acetate,     A represents a group chosen from the structures A1 to A19 below:     in which R₄ represents a C₁-C₄ alkyl radical which can be     substituted with a hydroxyl radical and R₅ represents a C₁-C₄ alkoxy     radical, with the proviso that when D represents —CH, when A     represents A₄ or A₁₃ and when R₃ is other than an alkoxy radical,     then R₁ and R₂ do not simultaneously denote a hydrogen atom;     -   b) the compounds of formula (II) below:         in which:

-   R₆ represents a hydrogen atom or a C₁-C₄ alkyl radical,

-   R₇ represents a hydrogen atom, an alkyl radical which can be     substituted with a —CN radical or with an amino group, a     4′-aminophenyl radical or forms with R₆ a heterocycle optionally     containing oxygen and/or nitrogen, which can be substituted with a     C₁-C₄ alkyl radical,

-   R₈ and R₉, which may be identical or different, represent a hydrogen     atom, a halogen atom such as bromine, chlorine, iodine or fluorine,     a C₁-C₄ alkyl or C₁-C₄ alkoxy radical or a —CN radical,

-   X⁻ represents an anion preferably chosen from chloride, methyl     sulphate and acetate,     B represents a group chosen from the structures B1 to B6 below:     in which R₁₀ represents a C₁-C₄ alkyl radical, R₁₁ and R₁₂, which     may be identical or different, represent a hydrogen atom or a C₁-C₄     alkyl radical;     -   c) the compounds of formulae (III) and (III′) below:         in which:

-   R₁₃ represents a hydrogen atom, a C₁-C₄ alkoxy radical, a halogen     atom such as bromine, chlorine, iodine or fluorine, or an amino     radical,

-   R₁₄ represents a hydrogen atom, a C₁-C₄ alkyl radical or forms, with     a carbon atom of the benzene ring, a heterocycle optionally     containing oxygen and/or substituted with one or more C₁-C₄ alkyl     groups,

-   R₁₅ represents a hydrogen atom or a halogen atom such as bromine,     chlorine, iodine or fluorine,

-   R₁₆ and R₁₇, which may be identical or different, represent a     hydrogen atom or a C₁-C₄ alkyl radical,

-   D₁ and D₂, which may be identical or different, represent a nitrogen     atom or a —CH group,

-   m=0 or 1,     it being understood that when R₁₃ represents an unsubstituted amino     group, then D₁ and D₂ simultaneously represent a —CH group and m=0,

-   X⁻ represents an anion preferably chosen from chloride, methyl     sulphate and acetate,

-   E represents a group chosen from the structures E1 to E8 below:     in which R′ represents a C₁-C₄ alkyl radical;     when m=0 and when D₁ represents a nitrogen atom, then E can also     denote a group of structure E9 below:     in which R′ represents a C₁-C₄ alkyl radical;     -   d) the compounds of formula (IV) below:         G-N═N-J  (IV)         in which:         the symbol G represents a group chosen from the structures G₁ to         G₃ below:         in which structures G₁ to G₃,

-   R₁₈ denotes a C₁-C₄ alkyl radical, a phenyl radical which can be     substituted with a

-   C₁-C₄ alkyl radical or a halogen atom chosen from chlorine, bromine,     iodine and fluorine;

-   R₁₉ denotes a C₁-C₄ alkyl radical or a phenyl radical;

-   R₂₀ and R₂₁, which may be identical or different, represent a C₁-C₄     alkyl radical, a phenyl radical or together form, in G₁, a benzene     ring substituted with one or more

-   C₁-C₄ alkyl, C₁-C₄ alkoxy or NO₂ radicals or together form, in G₂, a     benzene ring optionally substituted with one or more C₁-C₄ alkyl,     C₁-C₄ alkoxy or NO₂ radicals;

-   R₂₀ can also denote a hydrogen atom;

-   Z denotes an oxygen or sulphur atom or a group —NR₁₉;

-   M represents a —CH, —CR(R denoting C₁-C₄ alkyl) or —N⁺R₂₂(X⁻)_(r)     group;

-   K represents a —CH, —CR(R denoting C₁-C₄ alkyl) or —N⁺R₂₂(X⁻)_(r)     group;

-   P represents a —CH, —CR(R denoting C₁-C₄ alkyl) or —N⁺R₂₂(X⁻)_(r)     group; r denotes zero or 1;

-   R₂₂ represents an O⁻ anion, a C₁-C₄ alkoxy radical or a C₁-C₄ alkyl     radical;

-   R₂₃ and R₂₄, which may be identical or different, represent a     hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine     and fluorine, a C₁-C₄ alkyl or

-   C₁-C₄ alkoxy radical or an —NO₂ radical;

-   X⁻ represents an anion preferably chosen from chloride, iodide,     methyl sulphate, ethyl sulphate, acetate and perchlorate;     with the proviso that,

-   if R₂₂ denotes O⁻, then r denotes zero;

-   if K or P or M denote C₁-C₄—N⁺-alkyl X⁻, then R₂₃ or R₂₄ is other     than a hydrogen atom;

-   if K denotes —N⁺R₂₂(X⁻)_(r), then M=P=—CH, —CR;

-   if M denotes —N⁺R₂₂(X⁻)_(r), then K=P=—CH, —CR;

-   if P denotes —N⁺R₂₂(X⁻)_(r), then K=M and denote —CH or —CR;     -   if Z denotes a sulphur atom with R₂₁, denoting C₁-C₄ alkyl, then         R₂₀ is other than a hydrogen atom;     -   if Z denotes —NR₂₂ with R₁₉, denoting C₁-C₄ alkyl, then at least         one of the radicals R₁₈, R₂₀ or R₂₁ of the group of structure G₂         is other than a C₁-C₄ alkyl radical;         the symbol J represents:         (a) a group of         structure J₁ below:         in which structure J₁,

-   R₂₅ represents a hydrogen atom, a halogen atom chosen from chlorine,     bromine, iodine and fluorine, a C₁-C₄ alkyl or C₁-C₄ alkoxy radical,     a radical —OH, —NO₂, —NHR₂₈, —NR₂₉R₃₀, —N HCO(C₁-C₄)alkyl, or forms     with R₂₆ a 5- or 6-membered ring which may or may not contain one or     more hetero atoms chosen from nitrogen, oxygen and sulphur;

-   R₂₆ represents a hydrogen atom, a halogen atom chosen from chlorine,     bromine, iodine and fluorine, a C₁-C₄ alkyl or C₁-C₄ alkoxy radical     or forms with R₂₇ or R₂₈, a 5- or 6-membered ring which may or may     not contain one or more hetero atoms chosen from nitrogen, oxygen     and sulphur;

-   R₂₇ represents a hydrogen atom, an —OH radical, a radical —NHR₂₈ or     a radical —NR₂₉R₃₀;

-   R₂₈ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄     monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical or a     phenyl radical;

-   R₂₉ and R₃₀, which may be identical or different, represent a C₁-C₄     alkyl radical, a C₁-C₄ monohydroxyalkyl radical or a C₂-C₄     polyhydroxyalkyl radical;

-   (b) a 5- or 6-membered nitrogenous heterocyclic group which can     contain other hetero atoms and/or carbonyl groups and which can be     substituted with one or more C₁-C₄ alkyl, amino or phenyl radicals,     and in particular a group of structure J₂ below:     in which structure J₂,

-   R₃₁, and R₃₂, which may be identical or different, represent a     hydrogen atom, a C₁-C₄ alkyl radical or a phenyl radical;

-   Y denotes the —CO— radical or the radical

-   n=0 or 1, with, when n denotes 1, U denoting a —CO— radical.

In the structures (I) to (IV) defined above, the C₁-C₄ alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.

The cationic direct dyes of formulae (I), (II), (III) and (III′) which can be used in the dye compositions in accordance with the invention are known compounds and are described, for example, in patent applications WO 95/01772, WO 95/15144 and EP-A-0,714,954. Those of formula (IV) which can be used in the dye compositions in accordance with the invention are known compounds and are described, for example, in patent applications FR-2,189,006, FR-2,285,851 and FR-2,140,205 and its Certificates of Addition.

Among the cationic direct dyes of formula (I) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (I1) to (I54) below:

Among the compounds of structures (I1) to (I54) described above, the ones most particularly preferred are the compounds corresponding to the structures (I1), (I2), (I14) and (I31).

Among the cationic direct dyes of formula (II) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (II1) to (II9) below:

Among the cationic direct dyes of formula (III) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (III1) to (III18) below:

Among the specific compounds of structures (III1) to (III18) described above, the ones most particularly preferred are the compounds corresponding to the structures (III4), (III5) and (III13).

Among the cationic direct dyes of formula (III′) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (III′1) to (III′3) below:

Among the cationic direct dyes of formula (IV) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds of structures (IV)₁ to (IV)₇₇ below:

The cationic direct dye(s) used according to the invention preferably represent(s) from 0.001 to 10% by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.

(ii) The thickening polymer which can be used according to the present invention is chosen from the group consisting of:

-   -   (ii)₁—nonionic amphiphilic polymers comprising at least one         hydrophilic unit and at least one unit containing a fatty chain;     -   (ii)₂—anionic amphiphilic polymers comprising at least one         hydrophilic unit and at least one unit containing a fatty chain;     -   (ii)₃—cationic amphiphilic polymers comprising at least one         hydrophilic unit and at least one unit containing a fatty chain.

The nonionic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain (ii)₁, used according to the invention, are preferably chosen from:

-   -   (ii)₁(a) celluloses modified with groups comprising at least one         fatty chain; mention may be made, by way of example, of:         -   hydroxyethylcelluloses modified with groups comprising at             least one fatty chain, such as alkyl, arylalkyl or alkylaryl             groups or mixtures thereof, and in which the alkyl groups             are preferably C₈-C₂₂, such as the product Natrosol Plus             Grade 330 CS (C₁₆ alkyls) sold by the company Aqualon, or             the product Bermocoll EHM 100 sold by the company Berol             Nobel,         -   hydroxyethylcelluloses modified with groups comprising at             least one polyalkylene glycol alkylphenyl ether group, such             as the product Amercell Polymer HM-1500 (polyethylene             glycol (15) nonylphenyl ether) sold by the company Amerchol.     -   (ii)₁(b) hydroxypropylguars modified with groups comprising at         least one fatty chain, such as the product Esaflor HM 22 (C₂₂         alkyl chain) sold by the company Lamberti, and the products         Miracare XC95-3 (C₁₄ alkyl chain) and RE205-1 (C₂₀ alkyl chain)         sold by the company Rhône-Poulenc.     -   (ii)₁(c) polyurethane ethers comprising at least one fatty chain         such as C₈-C₃₀ alkyl or alkenyl groups, for instance the         products Dapral T 210 and Dapral T 212 sold by the company Akzo.     -   (ii)₁(d) copolymers of vinylpyrrolidone and of hydrophobic         monomers containing a fatty chain;         mention may be made, by way of example, of:         -   the products Antaron V216 or Ganex V216             (vinylpyrrolidone/hexadecene copolymer) sold by the company             I.S.P.         -   the products Antaron V220 or Ganex V220             (vinylpyrrolidone/eicosene copolymer) sold by the company             I.S.P.     -   (ii)₁(e) copolymers of C₁-C₆ alkyl methacrylates or acrylates         and of amphiphilic monomers comprising at least one fatty chain,         such as, for example, the oxyethylenated methyl         methacrylate/stearyl acrylate copolymer sold by the company         Goldschmidt under the name Antil 208.     -   (ii)₁(f) copolymers of hydrophilic methacrylates or acrylates         and of hydrophobic monomers comprising at least one fatty chain,         such as, for example, the polyethylene glycol         methacrylate/lauryl methacrylate copolymer.

The anionic amphiphilic polymers (ii)₂ can be chosen from those:

-   -   (ii)₂(a) comprising at least one hydrophilic unit and at least         one allyl ether unit containing a fatty chain, and preferably         from those in which the hydrophilic unit comprising an         unsaturated ethylenic anionic monomer, more particularly of a         vinylcarboxylic acid and most particularly of an acrylic acid, a         methacrylic acid or mixtures thereof, and in which the allyl         ether unit containing a fatty chain corresponds to the monomer         of formula (V) below:         CH₂═C R′CH₂O B_(n)R  (V)         in which R′ denotes H or CH₃, B denotes an ethylenoxy radical, n         is zero or denotes an integer ranging from 1 to 100, R denotes a         hydrocarbon-based radical chosen from alkyl and cycloalkyl         radicals comprising from 8 to 30 carbon atoms, preferably 10 to         24 and even more particularly from 12 to 18 carbon atoms, and         most particularly a C₁₀-C₂₄ alkyl radical.

One unit of formula (V) which is more particularly preferred according to the present invention is a unit in which R′ denotes H, n is equal to 10 and R denotes a stearyl (C₁₈) radical.

Anionic amphiphilic polymers of this type are described and prepared according to an emulsion polymerization process in patent EP-0,216,479 B2.

Among the said anionic amphiphilic polymers cited (ii)₂(a) it is particularly preferred according to the invention to use the polymers formed from 20 to 60% by weight of acrylic acid and/or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth)acrylates, from 2 to 50% by weight of allyl ether containing a fatty chain of formula (I), and from 0 to 1% by weight of a crosslinking agent which is a well known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

Among the latter polymers, the ones most particularly preferred are the crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (10 EO) stearyl ether (Steareth-10), in particular those sold by the company Allied Colloids under the names Salcare SC 80 and Salcare SC 90 which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of Steareth-10 allyl ether (40/50/10).

The anionic amphiphilic polymers (II)₂ can also be chosen from those:

-   -   (ii)₂(b) comprising at least one hydrophilic unit of unsaturated         olefinic carboxylic acid type, and at least one unit containing         a fatty chain exclusively of (C₁₀-C₃₀)alkyl ester of unsaturated         carboxylic acid type, and preferably from those in which the         hydrophilic unit of unsaturated olefinic carboxylic acid type         corresponds to the monomer of formula (VI) below:         in which formula R¹ denotes H or CH₃ or C₂H₅, i.e. acrylic acid,         methacrylic acid or ethacrylic acid units, and in which the unit         containing a fatty chain of (C₁₀-C₃₀)alkyl ester of unsaturated         carboxylic acid type corresponds to the monomer of formula (VII)         below:         in which formula R¹ denotes H or CH₃ or C₂H₅ (i.e. acrylate,         methacrylate or ethacrylate units) and preferably H (acrylate         units) or CH₃ (methacrylate units), R² denoting a C₁₀-C₃₀ alkyl         and preferably C₁₂-C₂₂ alkyl radical.

(C₁₀-C₃₀)alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic amphiphilic polymers of this type (ii)₂(b) are described and prepared, for example, according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

Anionic amphiphilic polymers (ii)₂(b) which can be used in the context of the present invention can more particularly denote polymers formed from a mixture of monomers comprising:

-   (i) essentially acrylic acid and an ester of formula (VII) described     above in which R¹ denotes H or CH₃, R² denoting an alkyl radical     containing from 12 to 22 carbon atoms, and a crosslinking agent,     such as, for example, those comprising 95 to 60% by weight of     acrylic acid (hydrophilic unit), 4 to 40% by weight of C₁₀-C₃₀ alkyl     acrylate (unit containing a fatty chain) and 0 to 6% by weight of     crosslinking polymerizable monomer, or 98 to 96% by weight of     acrylic acid (hydrophilic unit), 1 to 4% by weight of C₁₀-C₃₀ alkyl     acrylate (unit containing a fatty chain) and 0.1 to 0.6% by weight     of crosslinking polymerizable monomer, -   (ii) essentially acrylic acid and lauryl methacrylate, such as the     polymer formed from 66% by weight of acrylic acid and 34% by weight     of lauryl methacrylate.

The said crosslinking agent is a monomer containing a group with

at least one other polymerizable group whose unsaturated bonds are not conjugated to each other. Mention may be made in particular of polyallyl ethers such as, in particular, polyallylsucrose and polyallylpentaerythritol.

Among the said polymers cited in class (ii)₂(b), the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382 and even more preferably Pemulen TR1 and the product sold by the company S.E.P.C. under the name Coatex SX.

The cationic amphiphilic polymers (i)₃ used according to the invention are preferably chosen from quaternized cellulose derivatives and polyacrylates containing amino side groups.

The quaternized cellulose derivatives are, in particular,

-   -   (ii)₃(a) quaternized celluloses modified with groups comprising         at least one fatty chain, such as alkyl, arylalkyl or alkylaryl         groups comprising at least 8 carbon atoms, or mixtures thereof,     -   (ii)₃(b) quaternized hydroxyethylcelluloses modified with groups         comprising at least one fatty chain, such as alkyl, arylalkyl or         alkylaryl groups comprising at least 8 carbon atoms, or mixtures         thereof.

The polyacrylates containing amino side groups (ii)₃(C), which may or may not be quaternized, contain, for example, hydrophobic groups such as Steareth-20 [polyoxyethylenated (20) stearyl alcohol].

The alkyl radicals borne by the above quaternized celluloses or hydroxycelluloses preferably comprise from 8 to 30 carbon atoms.

The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

As examples of quaternized alkylhydroxyethyl-celluloses containing C₈-C₃₀ fatty chains, mention may be made of the products Quatrisoft LM200, Quatrisoft LM-X529-18-A, Quatrisoft LM-X529-18-B (C₁₂ alkyl) and Quatrisoft LM-X529-8 (C₁₈ alkyl) sold by the company Amerchol and the products Crodacel QM, Crodacel QL (C₁₂ alkyl) and Crodacel QS (C₁₈ alkyl) sold by the company Croda.

As examples of polyacrylates containing amino side chains, mention may be made of the polymers 8781-124B or 9492-103 from the company National Starch.

It is more particularly preferred, according to the present invention, to use the amphiphilic polymers of nonionic type (ii), and of anionic type (ii)₂ described above and even more particularly the amphiphilic polymers of class (ii)₁(a) and (ii)₂(c) and of class (ii)₂(a) and (ii)₂(b).

The amphiphilic thickening polymers of nonionic, anionic or cationic type used in the compositions of the present invention are preferably present in a proportion of from 0.01 to 10% by weight approximately, in particular in a proportion of from 0.1 to 5% by weight approximately, relative to the total weight of the dye composition applied to the keratin fibres.

The medium which is suitable for dyeing (or support) generally comprising water or of a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently water-soluble. As organic solvents, mention may be made, for example, of C₁-C₄ lower alkanols such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol, as well as similar products and mixtures thereof.

The solvents can be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition in accordance with the invention is generally approximately between 2 and 11 and preferably approximately between 5 and 10. It can be adjusted to the desired value using acidifying or basifying agents usually used for dyeing keratin fibres.

Among the acidifying agents, mention may be made, by way of example, of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.

Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (VIII) below:

in which W is a propylene residue optionally substituted with a hydroxyl group or a C₁-C₆ alkyl radical; R₃₃, R₃₄, R₃₅ and R₃₆, which may be identical or different, represent a hydrogen atom or a C₁-C₆ alkyl or C₁-C₆ hydroxyalkyl radical.

In addition to the cationic direct dye(s) (i) defined above, the dye composition in accordance with the invention can contain one or more additional direct dyes which can be chosen, for example, from nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthene dyes and azo dyes which are non-cationic.

When it is intended for oxidation dyeing, the dye composition in accordance 1: with the invention contains, in addition to the cationic direct dye(s) (i), one or more oxidation bases chosen from the oxidation bases conventionally used for oxidation dyeing and among which mention may be made in particular of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

When they are used, the oxidation base(s) preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately relative to this weight.

When it is intended for oxidation dyeing, the dye composition in accordance with the invention can also contain, in addition to the cationic direct dye (i) and the thickening polymer (ii) as well as the oxidation bases, one or more couplers so as to modify the shades obtained or to enrich them with glints, by using the cationic direct dye(s) (i) and the oxidation base(s).

The couplers which can be used in the dye composition in accordance with the invention can be chosen from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers.

When it is (they are) present, the coupler(s) preferably represent(s) from 0.0001 to 10% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 5% by weight approximately relative to this weight.

The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, surfactants, film-forming agents, ceramides, preserving agents, screening agents and opacifiers.

Needless to say, a person skilled in the art will take care to select this (these) optional complementary compound(s) such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.

The dye composition according to the invention can be in various forms, such as in the form of liquids, shampoos, creams or gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair. It can be obtained by mixing, at the time of use, a composition, which may be pulverulent, containing the cationic direct dye(s) with a composition containing the specific thickening polymer.

When the combination of the cationic direct dye (i) and the thickening polymer (ii) according to the invention is used in a composition intended for oxidation dyeing (in which case one or more oxidation bases are used, optionally in the presence of one or more couplers) or when it is used in a composition intended for lightening direct dyeing, then the dye composition in accordance with the invention also comprises at least one oxidizing agent chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases, lactases and two-electron oxidoreductases. It is particularly preferred to use hydrogen peroxide or enzymes.

Another subject of the invention is a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.

According to a first variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres, for a period which is sufficient to develop the desired coloration, after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried.

The time required to develop the coloration on the keratin fibres is generally between 3 and 60 minutes and even more specifically between 5 and 40 minutes.

According to a second variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres, for a period which is sufficient to develop the desired coloration, without final rinsing.

According to one specific embodiment of this dyeing process, and when the dye composition in accordance with the invention comprises at least one oxidation base and at least one oxidizing agent, the dyeing process comprises a first step which consists in separately storing, on the one hand, a composition (A1) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye (i) as defined above and at least one oxidation base, and, on the other hand, a composition (B1) comprising, in a medium which is suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, the composition (A1) or the composition (B1) containing the thickening polymer (ii) as defined above.

According to another specific embodiment of this dyeing process, and when the dye composition in accordance with the invention comprises at least one oxidizing agent, the dyeing process comprises a first step which consists in separately storing, on the one hand, a composition (A2) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye (i) as defined above, and, on the other hand, a composition (B2) comprising, in a medium which is suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, the composition (A2) or the composition (B2) containing the thickening polymer as defined above.

Another subject of the invention is a multi-compartment dyeing device or dyeing “kit” or any other multi-compartment packaging system, a first compartment of which comprises the composition (A1) or (A2) as defined above and a second compartment of which comprises the composition (B1) or (B2) as defined above. These devices can be equipped with means for dispensing the desired mixture onto the hair, such as the devices described in patent FR 2,586,913 in the name of the Applicant.

The examples which follow are intended to illustrate the invention without, however, limiting its scope.

EXAMPLES EXAMPLES 1 to 3

The three direct dyeing compositions given in the table below were prepared: (all contents expressed in grams) Example 1 Example 2 Example 3 Cationic direct dye of  0.2 formula (I1) Cationic direct dye of  0.2 formula (I14) Cationic direct dye of  0.1 formula (IV27) Diurethane (HMD) of oxy-  1.0 AM* ethylenated (66 EO) and oxy- propylenated (14 PO) C₁₆-C₁₈ alcohols, sold under the name Dapral T212 by the company Akzo Methacrylic acid/ethyl  1.0 AM* acrylate/Steareth 10 allyl ether crosslinked terpolymer sold as a 30% by weight emulsion under the name Salcare SC90 by the company Allied Colloid Acrylic acid/C₁₀-C₃₀ alkyl  1.0 AM* acrylate crosslinked copolymer sold under the name Pemulen TR1 by the company Goodrich Ethanol  10  10  10 2-Amino-2-methyl-1-propanol pH 9 pH 9 pH 9 qs Demineralized water qs 100 100 100 AM* denotes active material

The above compositions were each applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The locks of hair were then rinsed, washed with a standard shampoo and then dried.

were following shades: Examples Shades obtained 1 Bright red 2 Bright orange 3 Bright purple 

1. A ready-to-use composition for dyeing keratin fibers, comprising: (i) at least one cationic direct dye chosen from compounds of formulae (I), (II), (III), (III′) and (IV) below, and (ii) at least one thickening polymer; (a) wherein said compounds of formula (I) are chosen from compounds of formula:

in which: D is chosen from a nitrogen atom and a —CH group, R₁ and R₂, which may be identical or different, are chosen from a hydrogen atom; a 4′-aminophenyl radical; and C₁-C₄ alkyl radicals which can optionally be substituted with a radical chosen from —CN, —OH and —NH₂ radicals or form, with each other or a carbon atom of the benzene ring of formula (I), a heterocycle optionally containing a heteratom chosen from oxygen and nitrogen, which can be substituted with at least one radical chosen from C₁-C₄ alkyl radicals; R₁ and R₂ may form, with each other or with a carbon atom of the benzene ring of formula (I), a heterocycle optionally containing a heteroatom chosen from oxygen and nitrogen, which can be substituted with at least one radical chosen from C₁-C₄ alkyl radicals; R₃ and R′₃, which may be identical or different, are chosen from a hydrogen atom, halogen atoms, a cyano radical, C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals and acetyloxy radicals, X⁻ is chosen from anions, A is chosen from structures A₁ to A₁₉ below:

in which: R₄ is chosen from C₁-C₄ alkyl radicals which can be substituted with a hydroxyl radical, and R₅ is chosen from C₁-C₄ alkoxy radicals, and wherein when D represents —CH, when A represents A₄ or A₁₃ and when R₃ is not an alkoxy radical, R₁ and R₂ are not both a hydrogen atom; (b) wherein said compounds of formula (II) are chosen from compounds of formula:

in which: R₆ is chosen from a hydrogen atom and C₁-C₄ alkyl radicals, R₇ is chosen from a hydrogen atom, alkyl radicals which can be substituted with a species chosen from a —CN radical and an amino group, and a 4′-aminophenyl radical, or forms, with R₆, a heterocycle optionally comprising at least one heteroatom chosen from oxygen and nitrogen, which can be substituted with C₁-C₄ alkyl radicals, R₈ and R₉, which may be identical or different, are chosen from a hydrogen atom, halogen atoms, C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals and a —CN radical, X⁻ is chosen from anions, B is chosen from structures B₁ to B₆ below:

in which: R₁₀ is chosen from C₁-C₄ alkyl radicals, and R₁₁ and R₁₂, which may be identical or different, are chosen from a hydrogen atom and C₁-C₄ alkyl radicals; (c) wherein said compounds of formulae (III) and (III′) are chosen from compounds of formulae:

in which: R₁₃ is chosen from a hydrogen atom, C₁-C₄ alkoxy radicals, halogen atoms and an amino radical, R₁₄ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals or forms, with a carbon atom of the benzene ring, a heterocycle optionally containing an oxygen heteroatom and/or substituted with at least one radical chosen from C₁-C₄ alkyl radicals, R₁₅ is chosen from a hydrogen atom and halogen atoms, R₁₆ and R₁₇, which may be identical or different, are chosen from a hydrogen atom and C₁-C₄ alkyl radicals, D₁ and D₂, which may be identical or different, are chosen from a nitrogen atom and a —CH group, m=0 or 1, wherein when R₁₃ is an unsubstituted amino group, D₁ and D₂ are both a —CH group and m=0, X⁻ is chosen from anions, E is chosen from structures E₁ to E₈ below:

in which R′ is chosen from C₁-C₄ alkyl radicals; wherein when m=0 and when D, represents a nitrogen atom, E can be further chosen from structure E9 below:

in which R′ is chosen from C₁-C₄ alkyl radicals; (d) wherein said compounds of formula(IV) are chosen from compounds of formula: G-N═N-J  (IV) in which: G is chosen from structures G₁ to G₃ below:

in which: R₁₈ is chosen from C₁-C₄ alkyl radicals, a phenyl radical which can optionally be substituted with C₁-C₄ alkyl radicals and a halogen atom chosen from chlorine, bromine, iodine and fluorine; R₁₉ is chosen from C₁-C₄ radicals and a phenyl radical; R₂₀ and R₂₁, which may be identical or different, are chosen from C₁-C₄ alkyl radicals and a phenyl radical, or together form, in G₁, a benzene ring substituted with at least one radical chosen from C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals and NO₂ radicals, or together form, in G₂, a benzene ring optionally substituted with at least one radical chosen from C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals and NO₂ radicals; R₂₀ can be further chosen from a hydrogen atom; Z is chosen from an oxygen atom, a sulphur atom and —NR₁₉ radicals; M is chosen from a —CH radical, —C(C₁-C₄ alkyl) radicals and —N ⁺R₂₂(X⁻)_(r) radicals; K is chosen from a —CH radical, —C(C₁-C₄ alkyl) radicals and —N ⁺R₂₂(X⁻)_(r) radicals; P is chosen from a —CH radical, —C(C₁-C₄ alkyl) radicals and —N ⁺R₂₂(X⁻)_(r) radicals; wherein r denotes zero or 1; wherein R₂₂ is chosen from an O⁻ anion, C₁-C₄ alkoxy radicals, and C₁-C₄ alkyl radicals; R₂₃ and R₂₄, which may be identical or different, are chosen from a hydrogen atom, halogen atoms chosen from chlorine, bromine, iodine and fluorine, C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals and an —NO₂ radical; X⁻ is chosen from anions; wherein if R₂₂ is O⁻, r is zero; if K or P or M denote C₁-C₄—N⁺-alkyl X⁻, then R₂₃ or R₂₄ is other than a hydrogen atom; wherein if K is —N⁺R₂₂(X)_(r), M and P are the same and are chosen from a —CH radical and —C(C₁-C₄ alkyl) radicals; wherein if M denotes —N ⁺R₂₂(X⁻)_(r), K and P are the same and are chosen from a —CH radical and —C(C₁-C₄ alkyl) radicals; if P is —N ⁺R₂₂(X⁻)_(r), K and M are the same and are chosen from a —CH radical and —C(C₁-C₄ alkyl) radicals; if Z is a sulphur atom with R₂₁ being a radical chosen from C₁-C₄ alkyl radicals, R₂₀ is not a hydrogen atom; if Z is —NR₂₂ with R₁₉ being a radical chosen from C₁-C₄ alkyl radicals, at least one of the radicals R₁₈, R₂₀ and R₂₁ of G₂ is not chosen from C₁-C₄ alkyl radicals; J is chosen from: (1) radicals chosen from structure J₁ below:

in which: R₂₅ is chosen from a hydrogen atom, halogen atoms chosen from chlorine, bromine, iodine and fluorine, C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals, an —OH radical, an —NO₂ radical, —NHR₂₈ radicals, —NR₂₉R₃₀ radicals, —NHCO(C₁-C₄)alkyl radicals, or forms, with R₂₆, a 5- or 6-membered ring optionally containing at least one heteroatom chosen from nitrogen, oxygen and sulphur; R₂₆ is chosen from a hydrogen atom, halogen atoms chosen from chlorine, bromine, iodine and fluorine, C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals or forms, with R₂₇ or R₂₈, a 5- or 6-membered ring optionally containing at least one heteroatom chosen from nitrogen, oxygen and sulphur; R₂₇ is chosen from a hydrogen atom, an —OH radical, —NHR₂₈ radicals and —NR₂₉R₃₀ radicals; R₂₈ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals, C₁-C₄ monohydroxyalkyl radicals, C₂-C₄ polyhydroxyalkyl radicals and a phenyl radical; R₂₉ and R₃₀, which may be identical or different, are chosen from C₁-C₄ alkyl radicals, C₁-C₄ monohydroxyalkyl radicals and C₂-C₄ polyhydroxyalkyl radicals; and (2) 5- and 6-membered nitrogenous heterocyclic groups optionally containing other heteroatoms and/or carbonyl groups and optionally substituted with at least one radical chosen from C₁-C₄ alkyl radicals, an amino radicals, and phenyl radicals; and wherein said at least one thickening polymer is chosen from polymers comprising: (ii)₁—non-ionic amphiphilic polymers, comprising: at least one hydrophilic unit and at least one unit comprising a fatty chain; (ii)₂—anionic amphiphilic polymers, comprising: at least one hydrophilic unit and at least one unit comprising a fatty chain; and (ii)₃—cationic amphiphilic polymers, comprising at least one hydrophilic unit and at least one unit comprising a fatty chain. 2-107. (canceled) 